Perinone dyestuffs and process for preparing them

ABSTRACT

Dyestuffs consisting of the mixture of isomers of the formulae wherein R5 and R6 are hydrogen, alkyl or hydroxyalkyl with 1 to 4 carbon atoms or phenyl, or together are piperidine, morpholine or piperazine. The new dyestuffs are very suitable for the dyeing of synthetic materials such as polyethylene-glycol terephthalate, acetyl cellulose or polyamides. They yield brilliant greenish yellow to orange red shades which have a good fastness to light and to thermofixation. They are also very suitable for the dyeing of fibre-forming polymers such as for example polyethylene-glycol terephthalate in the mass. Furthermore, a big part of the dyestuffs can be used for dyeing synthetic fibre materials such as polyester fibers from organic solvents, for example perchloroethylene.   WHEREIN R1 is hydrogen, alkyl with 1 to 20 carbon atoms, alkoxyalkyl or alkoxycarbonyl each with up to 4 carbon atoms, benzyl, alkoxycarbonyl with up to 20 carbon atoms or phenyl, R2 is alkoxycarbonyl with up to 20 carbon atoms, cyano, alcanoyl, alkoxyalkoxycarbonyl each with up to 4 carbon atoms, carbonamido, phenylcarbonamido, mono- or dialkylcarbonamido with up to 8 carbon atoms or cyclohexylcarbonamido, R3 and R4 are identical and are hydrogen or alkoxy with 1 to 4 carbon atom atoms or R3 is alkoxy with 1 to 4 carbon atoms and R4 is hydrogen and R is phenylthio which may be substituted by one or two chlorine or bromine atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl groups and with up to 4 carbon atoms or a cyano, trifluoromethyl or nitro group; naphthylthio, pyridinethio, benzimidazolyl-2-thio, benzoxazolyl-2-thio, benzthiazolyl-2-thio or an amino group of the formula

United States Patent 1191 Troster Nov. 18, 1975 PERINONE DYESTUFFS AND PROCESS FOR PREPARING THEM [75] Inventor: Helmut Troster, Frankfurt am Main,

Germany [73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: Aug. 2, 1973 [21] Appl. No.: 384,794

[30] Foreign Application Priority Data Aug. 4, 1972 Germany 2238378 [52] US. Cl 260/283 S; 260/247.2 A; 260/247.2 B; 260/247.5 EP; 260/247.5 GP;

260/268 PC; 260/268 TR; 260/282;

260/283 CN; 260/287 CF; 260/288 CF [51] Int. CI. C07D 217/24 [58] Field of Search 260/283 S, 282, 288 CF [56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,071,386 6/1967 United Kingdom 260/282 Primary Examiner-Paul M. Coughlan, Jr. Assistant ExaminerMary C. Vaughn Attorney, Agent, or Firm-Curtis, Morris & Safford [57 ABSTRACT Dyestuffs consisting of the mixture of isomers of the formulae wherein R is hydrogen, alkyl with 1 to 20 carbon atoms, alkoxyalkyl or alkoxycarbonyl each with up to 4 carbon atoms, benzyl, alkoxycarbonyl with up to 20 carbon atoms or phenyl, R is alkoxycarbonyl with up I to 20 carbon atoms, cyano, alcanoyl, alkoxyalkoxycarbonyl each with up to 4 carbon atoms, carbonamido, phenylcarbonamido, monoor dialkylcarbonamido with up to 8 carbon atoms or cyclohexylcarbonamido, R and R are identical and are hydrogen or alkoxy with l to 4 carbon atom atoms or R is alkoxy with l to 4 carbon atoms and R, is hydrogen and R is phenylthio which may be substituted by one or two chlorine or bromine atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl groups and with up to 4 carbon atoms or a cyano, tritluoromethyl or nitro group; naphthylthio, pyridinethio, benzimidazolyl-Z-thio, benzoxazolyI-2- thio, benzthiazolyl2-thio or an amino group of the formula wherein R and R are hydrogen, alkyl or hydroxyalkyl with 1 to 4 carbon atoms or phenyl, or together are piperidine, morpholine or piperazine.

The new dyestuffs are very suitable for the dyeing of synthetic materials such as polyethylene-glycol terephthalate, acetyl cellulose or polyamides. They yield brilliant greenish yellow to orange red shades which have a good fastness to light and to thermofixation. They are also very suitable for the dyeing of fibre-forming 'polymers such as for example polyethylene-glycol terephthalate in the mass. Furthermore, a big part-of the dyestuffs can be used 5 Claims, No Drawings PERINONE DYESTUFFS AND PROCESS FOR PREPARING THEM and l wherein R is hydrogen, alkyl having 1 to 20 carbon atoms, alkoxyalkyl or alkoxycarbonyl having each up to 4 carbon atoms, benzyl, alkoxycarbonyl having up to 20 carbon atoms or phenyl, R is alkoxycarbonyl having up to 20 carbon atoms, acyl, cyano, alkoxyalkoxycarbonyl having each up to 4 carbon atoms, carbonamido, phenylcarbonamido, monoor dialkyl-carbonamido having up to 8 carbon atoms or cyclohexylcarbonamido, R and R are identical and represent hydrogen atoms or alkoxy having I to 4 carbon atoms or R is alkoxy having l to 4 carbon atoms and R is hydrogen and R is a phenylthio group which may be substituted by one or two chlorine or bromine atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl having each up to 4 carbon atoms or cyano, trifluoromethyl or nitro, naphthylthio, pyridinethio, benzimidazolyl-Z-thio, benzoxazolyl-2-thio, benzthiazolyl-Z-thio group or an amino group of the formula wherein R and R represent hydrogen, alkyl or hydroxyalkyl having 1 to 4 carbon atoms or phenyl, whereby NH2 m I I N o o N o I (III) R R R R 4 R a 4 X 3 wherein X is chlorine or bromine, with a compound of the formula [V (IV) and a carbonyl compound of the formula V R COCH R whereby, in the reaction with the carbonyl compound (V) the hydrozone obtained first having the formula VI or VII N 2 0K R T31 2 2 I l=C-CH R j& O N o (VI) (VII) subsequently was cyclized in the presence of basic condensation agents to give the pair of isomers of the formulae VIII and IX or X and XI R R R R and R have the above-mentioned meanings.

prepared in known manner by condensation of 4- chloroor 4-bromo-naphthalic acid anhydrides with equivalent amounts of hydrazine in inert organic solvents such as alcohols or acid dialkyl amides (J. Am. Soc. 82, 2728 [1960]).

The reaction of those compounds of the formula IV which have an -SH group with the compounds of the formula ill or X arid Xl is preferably carried out in the presence of at least the equivalent amount of an alkali acetate, hydroxide or -carbonate at an elevated temperature, preferably in an organic solvent, such as alcohol, pyridine or acid dialkyl amide. Examples for those mercapto compounds are thiopheno], 2- and 4-methyl-, 3,4-dimethyl-, 4-isopropyl-, 4-dodecyl-, 4-methoxy-, 3,4-dimethoxy-, 4-chloro-, 2,5-dichloro-. 4-bromo-, 2- methyl-5-chloro-, 2-methoxy-5-chloro-, 4-methylsulfonyl-, 4-methylsulfonyl, 3-eth0xycarbonyl-, 4-cyano-, 3-trifluoromethylthiophenol, oz-thionaphthol, '4-mercaptopyridine, 2-mercaptobenzthiazole, 6-methyl-2- mercapto-, 6-methoxy-2-mercaptoand 5-chloro-2- mercaptobenzthiazole, 2-mercaptobenzimidazole, 2- mercaptobenzoxazole.

For the reaction with an amine of the formula The starting compounds of the formula lll may be the compounds ill or X and XI are heated with an at least molar excess of the corresponding amine, if de' sired under pressure, to temperatures between about 100C and about 200C. The reaction time is about 1 to 8 hours. Condensation may also be carried out in a similar way in an organic solvent such as an acid dialkylamide, if desired in the presence of an acid-binding agent such as for example Na or potassium acetate. The product formed may be isolated in usual manner either directly or after diluting with water or a suitable "solvent having a low boiling point such as methanol.

Examples for these amines are aniline, o-toluidine, methyl and ethyl-aniline, 3-trifluoromethyl-aniline, 3- tetrafluoroethoxy-aniline, N-B-hydroxyethyl-aniline, 3-ethylaminotoluene, 3-B-hydroxyethylamino-toluene, dimethyl amine, dibutyl amine, di-(cyanethyl)-amine, di-(chloroethyl)-amine, diethanolamine, morpholine, 2,6-dimethyl-morpholine, piperidine, 4-methylpiperidine.

For the reaction with the carbonyl compound of the formula V the compounds of the formula ll or III are condensed at first with at least equivalent amounts of this carbonyl compound in the presence of about 0.01 to 0.1 mol of an acidic condensation agent per mol of starting compound. As acidic condensation agents may be considered aromatic sulfonic acids such as benzene or toluene-sulfonic acid, alkane-sulfonic acids such as ethane-sulfonic acid, amidosulfonic acid, sulfuric acid, phosphoric acid or gaseous hydrogen chloride. When using protic solvents such as acetic acid or propionic acid, these solvents already act as acidic condensation agent.

Condensation may be effected either in an inert organic solvent such as ethanol, isobutanol, monomethylglycol, acetic acid, chlorobenzene, dichlorobenzene, nitrobenzene, dimethyl formamide, N-methylpyrrolidone or directly with an excess of the carbonyl compound at a temperature of from about 80 C to about 200 C, if desired under pressure. The reaction time is between about minutes and 8 hours. In some cases it is suitable to remove the reaction water and other easily volatile by-products such as alcohol and acetone by distillation from the reaction mixture. After cooling the hydrazone formed may be isolated directly or after diluting with a solvent precipitating the hydrazone, such as for example methanol, glacial acetic acid or water.

toacetic acid -anilide, -p-anisidide, -3-chloro-anilide,

-5chloro-2-toluidide, -o-toluidide, -cyclohexylamide,

-octylamide, 2,4-dichlorobenzoylacetic acid amide.

The ringclosure of the hydrazone to form the pyrazol is expediently carried out in an organic solvent such as 'y-ethox- 5 5 butanol, isobutanol, pyridine, dimethyl sulfoxide, but

preferably in acid dialkyl amides such as dimethyl formamide, dimethyl acetamide, hexamethyl-phosphoric acid triamide or N-methylpyrrolidone in the presence of a basic compound such as sodium or potassium acetate, -carbonate or -hydroxide, piperidine,

morpholine or triethyl amine at a temperature of from about C and the boiling point of the solvent used.

If the hydrazone has already been prepared in an organic solvent of the above-mentioned type, it may be cycled directly in the reaction mixture, without previous isolation, after neutralization of the acidic condensation agent by addition of one of the bases mentioned. The product thus obtained may be isolated in usual manner.

The new dyestuffs are very suitable for the dyeing of synthetic materials such as polyethylene-glycol terephthalate, acetyl cellulose or polyamides. They yield brilliant greenish yellow to orange red shades which have a good fastness to light and to thermofixation. They are also very suitable for the dyeing of fibre-form ing polymers such as for example polyethylene-glycol terephthalate in the mass. Furthermore, a big part of the dyestuffs can be used for dyeing synthetic fibre materials such as polyester fibers from organic solvents, for example perchloroethylene.

In contradistinction to next comparable dyestuffs known from German patent specifications Nos. 1,279,260 and l,265,325 the products of the invention are distinguished by a better affinity to polyester and a better fastness of the dyeings to sublimation.

The following Examples illustrate the invention.

EXAMPLE 1 a. 64.0 Grams of 4-phenylthionaphthalic acid were stirred for 2 hours at C in g of acetacetic acid ethyl ester in the presence of 0.34 g of p-toluene-sulfonic acid, while passing thru a weak nitrogen stream. The clear solution was cooled to room temperature, diluted with 200 ml of methanol, and the crystallized light-yellow ethylester hydrazone was suction-filtered, washed with methanol and water and dried. The compound melted at l52l53C. lf instead of acetacetic acid ethyl ester the same amount of the corresponding methyl ester was used, the methylester hydrazone having a melting point of l 8 l-l 83C was obtained in analogous way.

b. A mixture of 86.4 g of the ethyl ester hydrazone obtained according to (a), 300 ml of dimethyl formamide and 0.4 g of anhydrous potassium acetate was kept at the boil for 1 hour. When cooling, the mixture of dyestuff isomers of the formulae was crystallized in golden-yellow crystals. The suspension was diluted with 300 ml of ethanol, suction-filtered, washed with water and dried.

Analysis: Calc: C, 69.6; H. 4.3; N, 6.8; S, 7.7. Found: C, 69.5; H, 4.5; N, 7.2; S, 7.6.

On polyester fabrics brilliant greenish-yellow dyeings were obtained having a very good fastness to light and to sublimation.

Dyeings having similar properties were obtained with the dyestuff obtained in the same manner from the methylester hydrazone.

c. The same mixture of dyestuff isomers was obtained when 21.6 g of the ethyl ester hydrazone obtained according to (a), 200 ml of ethylglycol monomethyl ether and 0.1 g of potassium hydroxide were cyclized for 1 hour at boiling temperature.

EXAMPLE 2 a. 75.0 Grams of acetylacetone were added to a mixture of 96.0 g of 4-phenylthionaphthalic acid hydrazide, 525 ml of isobutanol and 0.6 g of benzene-sulfonic acid and the mixture was kept at the boil for 3 hours. The hydrazone which crystallized, when cooling, in slightly yellow needles was suction-filtered, washed with methanol and water and dried. It melted at 197200C.

b. 10.0 Grams of the hydrazone obtained according to (a) were refluxed in 80 ml of isobutanol after addition of 0.2 g of anhydrous potassium acetate. The yellow mixture of dyestuff isomers precipitated having the formulae 1t c/CHa c 11 l o N c c N \Ir \C0CH3 CH5CO/ i 3 i S wassuction-filtered at room temperature, washed with methanol and water and dried.

Analysis: Calc: C, 7 l .8; H, 4.2; N, 7.3; S, 8.3. Found: C,71.9;H,4.3;N,7.3;S, 8.3.

The compound dyed polyester fibres in brilliant yellow shades which are distinguished by an excellent fastness to light and to sublimation.

c. A mixture of g of the hydrazone obtained according to (a), 30 g of dimethyl formamide and 0.5 g of piperidine was kept at the boil for 2 hours. The mixture of dyestuff isomers which crystallized when cooling was identical to the product obtained according to (b). Instead of piperidine the equivalent amount of morpholine or triethyl amine may be used with the same success as a catalyst.

EXAMPLE 3 a. A suspension of 25 g of 3-methoxy-4-(4- chlorophenyl-thio)-naphthalic acid hydrazide and 150 g of acetyl acetone was stirred for 1 hour at boiling temperature after addition of 0.25 g of toluene-sulfonic acid. The crystal suspension obtained when cooling was diluted with 200 ml of methanol and the yellow hydrazone was isolated in known manner.

b. 25 Grams of the compound obtained according to (a) were stirred for one hour at 140-145C in 75 g of N-methylpyrrolidone in the presence of 0.3 g of anhydrous sodium acetate.

100 Milliliters methanol were added to the cooled reaction mixture and the reddish yellow dyestuff of the formula (III c ts f c 11 I I 0 N C coca, c13 co which had precipitated was isolated in usual manner. Polyester fabrics were dyed with this mixture of isomers in brilliant golden yellow shades fast to light.

EXAMPLE 4 a. 16.0 Grams of 4-phenylthionaphthalic acid hydrazide, 35 g of acetoacetic acid anilide and 0.25 g of toluene-sulfonic acid were suspended in ml of chlorobenzene. The reaction mixture was refluxed for 3 hours. Then 35 ml of chlorobenzene were distilled off. The reaction product formed was crystallized slowly at room temperature. After diluting with ml of methanol stirring was continued for some hours, then the pale yellow hydrazone was suction-filtered, washed with methanol and water and dried.

b. 19.2 Grams of the hydrazone obtained according to (a), 58.0 g of dimethyl acetamide and 0.25 g of anhydrous potassium carbonate were heated for 30 min utes to 150C, the mixture was diluted with 100 ml of methanol at 2025C and the lemon-yellow pair of dyestuff isomers which had precipitated corresponding to the formulae N c/cns was precipitated in usual manner.

Analysis: Calc: C, 72.8; H, 4.1; N, 9.1; S, 6.9. Found: C, 72.8; H, 3.8; N, 9.3; S, 7.0.

On polyester fibres greenish yellow dyeings were obtained having a good fastness to light and to thermofixation.

EXAMPLE 5 a. 32.0 Grams of 4-phenylthionaphthalic acid hydra- 7 8 g of anhydrous potassium acetate was stirred for 15 cyclization product was crystallized at about 75C. It minutes at 145C. Then the mixture was diluted at consisted of the mixture of isomers of the formulae 2025C with 50 ml of methanol.

The crystallized reddish yellow dyestuff of the formula 5 N c c N l I l l 2 on ooccn O N G C o a 1 COCH 011 00 0 c coocrr, c o

3 Q 5 Analysis: Calc: c1. 11,4; N. 9.0. Found: 01, 11,6; N,

c. The mixture of pyrazolisomers obtained according to (b) could be prepared without intermediate isolation of the hydrazone obtained according to (a). when the had an excellent affinity to polyester fibre materials. It reaction was carried out as follows: 51221: 3323232 12 2? a very good fasmess to 24.6 Grams of 4-chloronaphthalic acid hydrazide, 20.0 g of acetyl acetone and 0.24 g of toluene-sulfomc Analysls: Cale: 65'4; Found: acid were refluxed and kept at the boil for 2 hours. 646; Then 0.15 g of potassium carbonate and 0.5 g of anhydrous potassium acetate was added at 80C and again EXAMPLE 6 2 kept at the boil for 2 hours. The mixture of pyrazoliso- 1 r 1 'thth d tbt' d d' a. 32.0 Grams of 4-phenylthionaphthalic acid hydra- 2 :3 epm 0 am accor mg Zide g of benzoyl acetone and g of toluene' d. 9.8 Grams of 2 S-dichlorothiophenol were added sulfonic acid were stirred in 120 ml of o-dichlorobento a mixture of g of the mixture of isomers Zene for 2 hours at 1 The lemon-yeilow tained according to (b) and 10.0 g of anhydrous potasdraz9ne formed havmg,a meltmg pomt of 199 2 C sium acetate in 150 ml of ethylene-glycol-monomethyl was F as usual wnh 100 ml of methanol ether, and the mixture was stirred for l hour at boiling Analysts: Cale: fl temperature. The crystallized yellow mixture of dye- B. 32.4 Grams of the hydrazone obtamed accordmg Stuff isomers of the formulae to (a) were cyclized according to Example 5(b). The 1 mixture of dyestuff isomers formed of the formula N a 6 N O N C /C N 0 cocn CH CO O 0 n=c c=n I I P o 11 c c 11 o cocn cH;,c0 01 S 01 8 5 (:1 i) i) was isolated in usual manner. Polyester fabrics could be dyed in brilliant yellow shades fast to light and to sublimation. if instead of 2,5dichlorothiophenol the equivalent amount of 4-methyl-3,4-dimethoxy, 2-methyl-5- chloro, 4-bromo-or 3-ethoxythiophenol was used, yeldyed polyester fabrics in brilliant greenish yellow low pairs of dyestuff isomers were obtained having simshades. The dyeings were distinguished by a very good ilar tinctorial properties.

f t t l t d t fastnessto l ght and an excellent as ness 0 1gh an 0 EXAMPLE 8 thermoflxation.

24.6 Grams of 4-chloronaphthalic acid hydrazide, EXAMPLE 7 20.0 g of acetyl acetone and 0.24 g of toluene-sulfonic acid were refluxed in 250 ml of isobutanol for 2 hours. Then 20.0 g of anhydrous potassium acetate and 12.0 g of thiophenol were added to the reaction mixture at a. A mixture of 24.6 g of 4-chloronaphthalic acid hy- 6 drazide, 20.0 g of acetyl acetone and 100 ml of acetic acid was refluxed for 2 hours. The brownish crystal room temperature, and the mixture was kept again at powder was suction-filtered, washed with glacial acetic the boil. Finally 7 g of potash were added at 70C and acid and dried. After recrystallization from ethylenethe whole was stirred at boiling temperature for 1 hour. glycol-monomethyl ether slightly brownish crystals The dyestuff formed was identical with the dyestuff obwere obtained which melted at 21 12l3C. tained according to Example 2(b).

b. 20.4 Grams of the hydrazone obtamed accordmg EXAMPLE 9 to (a) were refluxed with 61.2 g of dimethyl formamide and 0.2 g of anhydrous potassium carbonate for 30 minutes. When cooling, the slightly brownish yellow 21. 8 Drops of concentrated sulfuric acid were added to a mixture of 29.1 g of 4-bromonaphthalic acid hydrazide and 32.5 g of benzoyl acetone in 100 ml of chlorobenzene. The reaction mixture was stirred for one hour at boiling temperature. After cooling the mixture was diluted with 100 ml of methanol and the nearly colorless hydrazone crystallized was isolated in usual manner. It was cyclized according to Example 7(b) to form the mixture of pyrazolisomers of the formulae dyed on polyester materials a clear greenish yellow having a very good fastness to light and to sublimation.

EXAMPLE lo a. 0.25 Grams of toluene-sulfonic acid was added to a mixture of 18.5 g of 4-(benzimidazolo-2-thio)-naphthalic acid hydrazide and 75.5 g of acetyl acetone, and the mixture was heated to the boil for 30 minutes. At 70C the reaction mixture was diluted with 80 ml of methanol. The light-yellow hydrazone formed was isolated as usual. 1t melted at 268C under decomposition.

b. 9.2 Grams of the hydrazone obtained according to (a) and 0.2 g of anhydrous potassium acetate were stirred in 35 ml of dimethyl formamide for 10 minutes at 145C. The mixture was diluted at -25C with 30 ml of methanol. The crystallized reddish yellow mixture of isomers of the formula b. 21.5 Grams of the mixture of isomers obtained ac- 20 cording to (a) and 10.0 g of anhydrous potassium carbonate were suspended in 240 ml of butanol. After CH6 CH6 adding 13.5 g of 4-methylthiophenol the mixture was N c c N refluxed for 3 hours. The yellow dyestuff mixture obl t I I tained of the formula O H C C N O cocll cn co Q (l 11 a c Q I l N o S c0036 cil co /g SAN I dyed polyester with a clear yellow fast to sublimation. The following Table lists further dyestuffs which have been obtained according to the methods described in CH; the above Examples:

V Shade Example R, R2 R R4 R (polyester) 11 cH -CO0C3H1 H cl greenish yellow 12 CH 1 COOC4H9 H H greenish yellow l 3 -CH, --C00C,H OCH H yellow 14 ---CH; -COOCH 1 OCH; H :3 IOCHQ reddish yellow OCH l s -c H,. c00c.H H H yellow Cl 4 16 CH, COOC2H5 H H CN greenish yellow 17 -cH, -COOC,H H H -"SOCH;, greenish yellow oC,H, 1% --CH -C00C.H H H yellow continued Shade Example R R1 R;, R R (polyester) 44 cooC,H COCH H H ellow 45 -cH ccH COOCH H H -cl reenish ellow 46 -cH co0c,H5 co0c H H H 3 ellow \COOC,H 47 CHZCOOCHJ COOCHH OCH H reddish yellow 4% CH3 coNH-ocH H H greenish ellow Cl 9 Cl-l CONH H H greenish ellow 4 Cl so -cH CONH- H H reenish ellow SI CHJ CON H H greenlsh yellow c H s2 cH coNH H H reenish yellow 53 cll '-coNllc,.H., H H reenish yellow 54 cH COCH H H N yellow 55 CH; COOCzHqOCzH; H H greenish yellow 56 CH;. COOCzHqOCgH; H H Cl greenish yellow 57 CH COOCHzCHgOCHg H H greenish yellow 53 :Ha c0o(cH,)..cHa H H greenish ellow 59 --CH -COO(CH,)r ',CH H H 0 Cl greenish ellow 60 CH; COO(CH CHe H H Cl greenish yellow 6| cH -coocH,cH cH,) c- H H greenish ellow Z BI 62 -(CH:) eCH, COOCZH5 H H greenish yellow 63 (CH CH COOCQH; H H Q greenish yellow 65 was distilled off. The crystallized golden yellow hydra- EXAMPLE 64 a. 29.7 Grams of 4-morpholino-naphthalic acid hydrazide were kept at the boil with 20.0 g of acetyl acetone and 0.24 g of toluene-sulfonic acid in ml of chlorobenzcne for 30 minutes, while the reaction water zone was suction-filtered at room temperature, washed with methanol and water and dried.

b. 50.0 Grams of the hydrazone obtained according to (a) were suspended in g of dimethyl formamide and after addition of 0.5 g of potassium acetate refluxed for 30 minutes. The dyestuff mixture of the formulae N c N I I I 1 0 N C N O which crystallized when cooling, was suction-filtered,

after diluting with methanol, washed with methanol and water and dried. From methyl glycol the com pound crystallized in brilliant orange crystals,

Analysis: Calc: C, 69.8; H, 5.2; N, 11.6. Found: C, 69.5;H,5.4;N, 11.8. With this dyestuff polyester materials could be dyed in brilliant orange shades having a good fastness to light and to sublimation.

EXAMPLE 65 If the reaction was carried out as indicated in Example 64(a) and (b), but the 4-morpholino-naphthalic acid hydrazide was replaced by the equivalent amount of 3-methoxy-4-morpholinonaphthalic acid hydrazide, the red dyestuff mixture of the following formulae was obtained which dyed polyester fibres in brilliant orange red shades.

EXAMPLE 66 If in Example 64(a) 20.0 g of acetyl acetone were replaced by 32.5 g of benzoyl acetone and the reaction was carried out in analogous manner, the corresponding lemon-yellow hydrazone was obtained which could be cyclized according to (b) to the orange pair of dyestuff isomers of the formulae r N =0 e N N c N .o

cN.,,co V

l by, o

On polyester fabrics brilliant orange yellow dyeings were obtained, which were distinguished by a good fastness to light and an excellent fastness to sublimation.

EXAMPLE 67 A mixture of 9.3 g of the naphthoylene pyrazole obtained according to Example 7(b), 15.0 g of morpholine and 2.0 g of N-rnethyl pyrrolidone was refluxed for 1 hour. When cooling, the orange pair of dyestuff isomers was crystallized. It was identical with the product obtained according to Example 64(b).

EXAMPLE 68 a. 26.0 Grams of 4-(2',6-dimethylmorpholino)- naphthalic acid hydrazide, 70.0 g of acetoaeetic acid ethyl ester and 0.22 g of toluene-sulfonic acid were converted into the corresponding yellow hydrazone as described in Example 1(a).

b. 25.0 g of this hydrazone were cyclized as indicated in Example 64(b) in 50.0 g of dimethyl acetamide in the presence of 0.25 g of anhydrous potassium acetate to give the mixture of dyestuff isomers of the formulae N l a, I 0 015 CH o CH3 Polyester materials could be dyed in brilliant orange shades having good fastness properties.

EXAMPLE 69 4.0 Grams of 4-(4-methylphenylamino)-naphthalic acid hydrazide obtained by condensation of 4- bromonaphthalic acid hydrazide with 4-arninotoluene, were kept at the boil for 1 hour in 20 ml of acetyl acetone in the presence of 0.04 g of toluene-sulfonic acid. After cooling the mixture was diluted with 40 ml of methanol and the brownish-yellowhydrazone which crystallized slowly was isolated in known manner. After addition of 0.02 g of anhydrous potassium acetate 2.0 g of this hydrazone were converted with 2.0 g of dimethyl 17 18 formamide, by boiling for 10 minutes, into the red dye- Polyester fibres could be dyed in reddish orange stuff mixture of the formula j shades.

N C c i g i The following Table contains further Examples of I CH C N 5 dyestuffs which can be obtained in analogy to the N c r above Examples.

3Com CH 00 R1 1r e c l 0 N c NH i R2 isomers R4 6 CH: R

Shade Example R R2 R1 R4 R (polyester) CH;, COOCHB (I H H 41 1 orange yellow 71 CH 7 I COOC2H5 I h H H N f) orange yellow 72 CH; COOC4H9 H H N t) orange yellow 73 COOC2H5 H H N/' \O orange yellow 74 v -cH '-c00c H ocH H orange red 75 cH I COOQH, H H NH orange 76 co H H 41C}; I 77 CH;, CONH-Q H H -NO) orange yellow 78 CH COOCH COOCH; H H N O orange yellow orange 1 We claim:

1. Dyestuffs consisting of the mixture of isomers of the formulae 1 1\ g c= N O I O R and R C N R R R 4 3 wherein R is hydrogen, alkyl with l to 20 carbon atoms, alkoxyalkyl or alkoxycarbonyl each with up to 4 carbon atoms, benzyl, alkoxycarbonyl with up to 20 carbon atoms or phenyl, R is alkoxycarbonyl with up to 20 carbon atoms, cyano, alkanoyl, alkoxyalkoxycarbonyl each with up to 4 carbon atoms, carbonamido, phenylcarbonamido, monoor dialkylcarbonamido with up to 8 carbon atoms or cyclohexylcarbonamido, R and R are identical and are hydrogen or alkoxy with l to 4 carbon atoms or R is alkoxy with 1 to 4 carbon atoms and R is hydrogen and R is phenylthio which may be substituted by one or two chlorine or bromine atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl groups each with up to 4 carbon atoms or a cyano, trifluoromethyl or nitro group, naphthylthio, pyridinethio, benzimidazolyl-Z-thio, benzoxazolyl-Z-thio or benzthiazolyl-2-thio.

2. Dyestuffs as claimed in claim 1 consisting of the mixture of isomers of the formulae l N c: N

l i i i o and 4 i 4 R3 R3 wherein R is and, wherein R and R are hydrogen, chlorine or bromine, alkyl or alkoxy with l to 4 carbon atoms; R

is alkyl with l to 4 carbon atoms, R is carbalkoxy or alkanoyl with up to 4 carbon atoms and R and R are as defined in claim 10.

3. The dyestuff consisting of the mixture of isomers of the formulae CH CH N=C N I I I 0 //C\ /C\ COQC H CZHSOOC and 4. The dyestuff consisting of the mixture of isomers of the formlae /CH3 H3C\ c- N I I I 0 N c c /o COOCZHS H c ooc and I 5. The dyestuff consisting of the mixture of isomers of the formulae CH CH l I O N /C\ N o COCHa ca co and 

1. DYESTUFFS CONSISTING OF THE MIXTURE OF ISOMERS OF THE FORMULAE
 2. Dyestuffs as claimed in claim 1 consisting of the mixture of isomers of the formulae
 3. The dyestuff consisting of the mixture of isomers of the formulae
 4. The dyestuff consisting of the mixture of isomers of the formlae
 5. The dyestuff consisting of the mixture of isomers of the formulae 